Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3184
標題: 低介電polybenzoxazine/氰酸酯及高玻璃轉移溫度polybenzoxazine/雙馬來醯亞胺共聚物之合成與物性探討
Synthesis and properties of low-dielectric polybenzoxazines/cyanate ester and high-Tg polybenzoxazine/bismaleimide copolymers
作者: 馮裕仁
Feng, Yu-Ren
關鍵字: 氧代氮代苯并環己烷;benzoxazine;氰酸酯;雙馬來醯亞胺;cyanate ester;bismaleimide
出版社: 化學工程學系所
引用: [1]Holly, F. W.; Cope, C. J. Amer. Chem. Soc., 1944, 66, 1875. [2]Burke, W. J. J. Amer. Chem. Soc., 1949, 71, 609. [3]Ning, X.;Ishida, H. J. Polym. Sci., Part A: Polym. Chem. 1994,32,1121. [4]Brunovska, Z.;Ishida, H.;Liu, J.P. Macromol. Chem. Phys. 1999, 200,1745. [5]Lin, C.H.;Chang, S.L.;Hsieh, C.W. Polymer. 2008, 49, 1220 [6]Takeichi, T.; Saito, Y.; Agag, T; Muto, H.; Kawauchi, T. Polymer. 2008, 49, 1173 [7]Kiskan, B.; Demiray, G.; Yagci, Y. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 3512 [8]Takeichi ,T.; Kano, T.; Agag, T. Polymer. 2005, 46, 12172. [9]Lin, C.H. ; Chang, S.L. , Shen, T.Y.; Shih, Y.S.; Lin, H.T.; Wang, C.F. Polym. Chem., 2012, 3, 935. [10]Robert, A.;Albertus, P. H.J. Schenning.;Meijer, E.W. J. Polym. Sci., Part A: Polym. Chem. 2009, 47,4215. [11]Liu, W.B.;Qiu, Q.;Wang, J;Huo, Z.;Sun, H. Polymer. 2008, 49, 4399. [12]Liu, Y.L.;Chang, C.Y.;Hsu, C.Y.;Tseng, M.C.;Chou, C.I. J. Polym. Sci., Part A: Polym. Chem. 2010, 48, 4020. [13]Chang, H.C.; Lin, C.H.; Tian, Y.W.; Feng, Y.R.; Chan, L.H. J. Polym. Sci., Part A: Polym. Chem. 2012, 50, 2010. [14]Shieh, J.Y.; Yang, S.P.; Wu, M.F.; Wang, C.S. J. Polym. Sci., Part A: Polym. Chem. 2004, 42, 2589. [15]Marvel, C.S; Tarkoy, N. J. Amer. Chem. Soc. 1957, 59, 6000. [16]Katagirl, T.; Eguchi, K.Y. US Pat. 7994270 B2, to Sekisui chemical Co. Ltd., 2011.
摘要: 
1.主鏈型polybenzoxazine的前驅物P(B-bapf)是以9,9''-bis(4-aminophenyl)fluorene(Bapf)、Bisphenol A(BPA)與formaldehyde進行Mannich縮合聚合反應合成出來。縮合聚合的溶劑效應先前已檢視過,我們發現在眾多溶劑中,以Toluene/Ethanol為溶劑製備出的polybenzoxazine前驅物有最好的純度以及較高的分子量。我們將探討P(B-bapf)與dicyanate ester of bisphenol A (BACY)混合後固化的熱性質與介電性質,並以DSC和IR追蹤並探討其混合後的固化反應。混合後的性質也會作一系列探討。
2.以傳統法無法製備出含OH官能基的benzoxazine,在改用三步法後已成功地合成出來,方法是利用4-aminophenol以及
5,5''-methylenebis(2-hydroxybenzaldehyde)進行縮合反應,並以NaBH4還原imine後,進行縮合閉環。而原料
5,5''-methylene-bis(2-hydroxybenzaldehyde)是
2-hydroxybenzaldehyde與s-trioxane在硫酸環境下反應得到。
pOH-Bz與F-a(以bisphenol A/aniline/formaldehyde合成的
Benzoxazine)結構相似均含有兩個OH基,我們可以利用OH基為
反應點去和epoxy以及
1,1’-(methylenedi-p-phenylene)bismaleimide(DDM-BMI)進行反應。本論文將會以pOH-Bz/epoxy、F-a/epoxy、pOH-Bz/DDM-BMI、
F-a/DDM-BMI一系列系統進行比較討論。

1.A main-chain type polybenzoxazine precursor, P(B-bapf) was synthesized from the Mannich-type polycondensation of 9,9-bis(4-aminophenyl)fluorene (Bapf), bisphenol A(BPA), and formaldehyde. The solvent effect on the polycondensation was examined. We found that polybenzoxazine precursor prepared in toluene/ethanol exhibit the best purity and higher molecular weight, among the solvents we have tried. We investigated the curing behaviors, thermal and dielectric properties of the blends of P(B-bapf) and dicyanate ester of bisphenol A(BACY). DSC and IR were applied to monitor the curing reactions of the reactive blends, and the reactions in the reactive blends were discussed. The properties of the blend were also investigated.
2.Phenolic OH-containing benzoxazine (p-OHBz), which cannot be easily prepared by traditional procedures, have successfully been prepared. p-OHBz was prepared from the condensation of 4-aminophenol and 5,5''-methylenebis(2-hydroxybenzaldehyde), reducing the resulting imine linkage by NaBH4, and ring closure condensation. The key starting material, 5,5''-methylenebis(2-hydroxybenzaldehyde), was prepared from 2-hydroxybenzodehyde and s-trioxane in the presence of sulfuric acid. p-OHBz is structurally similar to bis(3,4-dihydro-2H-3-phenyl-1,3-benzoxazinyl)methane (F-a, a benzoxizne based on bisphenol F/aniline/formaldehyde) except for the two phenolic OHs. The phenolic OHs can provide a reaction site with epoxy and 1,1''-(methylenedi-p-phenylene)bismaleimide (DDM-BMI). The structure-property relationships between p-OHBz/epoxy, F-a/epoxy, p-OHBz/DDM-BMI, F-a/DDM-BMI copolymers were discussed.
URI: http://hdl.handle.net/11455/3184
其他識別: U0005-0808201217141400
Appears in Collections:化學工程學系所

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